This document provides information about the iron-carbon phase diagram and the microstructures that form in steels based on their carbon content and heat treatments. It discusses the various phases in the Fe-C system including ferrite, austenite, cementite, and martensite. It also summarizes how heating and cooling rates can affect phase transformations through phenomena like supercooling and influence the resulting microstructures like pearlite, bainite, and spheroidite. The mechanical properties of different microstructures are also addressed, with martensite described as the hardest and most brittle.

1. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 1
Iron-Carbon Phase
Diagram (a review) see
Callister Chapter 9

2. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 2
The Iron–Iron Carbide (Fe–Fe3C) Phase Diagram
In their simplest form, steels are alloys of Iron (Fe) and
Carbon (C). The Fe-C phase diagram is a fairly complex
one, but we will only consider the steel part of the diagram,
up to around 7% Carbon.

3. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 3
Phases in Fe–Fe3C Phase Diagram
α-ferrite - solid solution of C in BCC Fe
• Stable form of iron at room temperature.
• The maximum solubility of C is 0.022 wt%
• Transforms to FCC γ-austenite at 912 °C
γ-austenite - solid solution of C in FCC Fe
• The maximum solubility of C is 2.14 wt %.
• Transforms to BCC δ-ferrite at 1395 °C
• Is not stable below the eutectic temperature
(727 ° C) unless cooled rapidly (Chapter 10)
δ-ferrite solid solution of C in BCC Fe
• The same structure as α-ferrite
• Stable only at high T, above 1394 °C
• Melts at 1538 °C
Fe3C (iron carbide or cementite)
• This intermetallic compound is metastable, it
remains as a compound indefinitely at room T, but
decomposes (very slowly, within several years)
into α-Fe and C (graphite) at 650 - 700 °C
Fe-C liquid solution

4. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 4
A few comments on Fe–Fe3C system
C is an interstitial impurity in Fe. It forms a solid solution
with α, γ, δ phases of iron
Maximum solubility in BCC α-ferrite is limited (max.
0.022 wt% at 727 °C) - BCC has relatively small interstitial
positions
Maximum solubility in FCC austenite is 2.14 wt% at 1147
°C - FCC has larger interstitial positions
Mechanical properties: Cementite is very hard and brittle -
can strengthen steels. Mechanical properties also depend
on the microstructure, that is, how ferrite and cementite are
mixed.
Magnetic properties: α -ferrite is magnetic below 768 °C,
austenite is non-magnetic
Classification. Three types of ferrous alloys:
• Iron: less than 0.008 wt % C in α−ferrite at room T
• Steels: 0.008 - 2.14 wt % C (usually < 1 wt % )
α-ferrite + Fe3C at room T (Chapter 12)
• Cast iron: 2.14 - 6.7 wt % (usually < 4.5 wt %)

5. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 5
Eutectic and eutectoid reactions in Fe–Fe3C
Eutectoid: 0.76 wt%C, 727 °C
γ(0.76 wt% C) ↔ α (0.022 wt% C) + Fe3C
Eutectic: 4.30 wt% C, 1147 °C
L ↔ γ + Fe3C
Eutectic and eutectoid reactions are very important in
heat treatment of steels

6. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 6
Development of Microstructure in Iron - Carbon alloys
Microstructure depends on composition (carbon
content) and heat treatment. In the discussion below we
consider slow cooling in which equilibrium is maintained.
Microstructure of eutectoid steel (I)

7. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 7
When alloy of eutectoid composition (0.76 wt % C) is
cooled slowly it forms perlite, a lamellar or layered
structure of two phases: α-ferrite and cementite (Fe3C)
The layers of alternating phases in pearlite are formed for
the same reason as layered structure of eutectic structures:
redistribution C atoms between ferrite (0.022 wt%) and
cementite (6.7 wt%) by atomic diffusion.
Mechanically, pearlite has properties intermediate to soft,
ductile ferrite and hard, brittle cementite.
Microstructure of eutectoid steel (II)
In the micrograph, the dark areas are
Fe3C layers, the light phase is α-
ferrite

8. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 8
Compositions to the left of eutectoid (0.022 - 0.76 wt % C)
hypoeutectoid (less than eutectoid -Greek) alloys.
γ → α + γ → α + Fe3C
Microstructure of hypoeutectoid steel (I)

9. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 9
Hypoeutectoid alloys contain proeutectoid ferrite (formed
above the eutectoid temperature) plus the eutectoid perlite
that contain eutectoid ferrite and cementite.
Microstructure of hypoeutectoid steel (II)

10. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 10
Compositions to the right of eutectoid (0.76 - 2.14 wt % C)
hypereutectoid (more than eutectoid -Greek) alloys.
γ → γ + Fe3C → α + Fe3C
Microstructure of hypereutectoid steel (I)

11. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 11
Hypereutectoid alloys contain proeutectoid cementite
(formed above the eutectoid temperature) plus perlite that
contain eutectoid ferrite and cementite.
Microstructure of hypereutectoid steel (II)

12. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 12
How to calculate the relative amounts of proeutectoid
phase (α or Fe3C) and pearlite?
Application of the lever rule with tie line that extends from
the eutectoid composition (0.76 wt% C) to α – (α + Fe3C)
boundary (0.022 wt% C) for hypoeutectoid alloys and to (α
+ Fe3C) – Fe3C boundary (6.7 wt% C) for hypereutectoid
alloys.
Fraction of α phase is determined by application of the
lever rule across the entire (α + Fe3C) phase field:

13. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 13
Example for hypereutectoid alloy with composition C1
Fraction of pearlite:
WP = X / (V+X) = (6.7 – C1) / (6.7 – 0.76)
Fraction of proeutectoid cementite:
WFe3C = V / (V+X) = (C1 – 0.76) / (6.7 – 0.76)

14. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 14
Phase Transformations
of Fe-C (a review)
see Callister Chapter 10

15. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 15
Phase transformations (change of the microstructure) can
be divided into three categories:
Phase transformations. Kinetics.
Diffusion-dependent with no change in phase
composition or number of phases present (e.g.
melting, solidification of pure metal, allotropic
transformations, recrystallization, etc.)
Diffusion-dependent with changes in phase
compositions and/or number of phases (e.g. eutectoid
transformations)
Diffusionless phase transformation - produces a
metastable phase by cooperative small displacements of
all atoms in structure (e.g. martensitic transformation
discussed in later in this chapter)
Phase transformations do not occur instantaneously.
Diffusion-dependent phase transformations can be rather
slow and the final structure often depend on the rate of
cooling/heating.
We need to consider the time dependence or
kinetics of the phase transformations.

16. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 16
Most phase transformations involve change in composition
⇒ redistribution of atoms via diffusion is required.
The process of phase transformation involves:
Kinetics of phase transformations
Nucleation of of the new phase - formation of stable small
particles (nuclei) of the new phase. Nuclei are often formed at
grain boundaries and other defects.
Growth of new phase at the expense of the original phase.
S-shape curve: percent of
material transformed vs.
the logarithm of time.
)exp(1 n
kty −−= Avrami Equation

17. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 17
Superheating / supercooling
Upon crossing a phase boundary on the composition-
temperature phase diagram phase transformation
towards equilibrium state is induced.
But the transition to the equilibrium structure takes time
and transformation is delayed.
During cooling, transformations occur at temperatures
less than predicted by phase diagram: supercooling.
During heating, transformations occur at temperatures
greater than predicted by phase diagram: superheating.
Degree of supercooling/superheating increases with rate
of cooling/heating.
Metastable states can be formed as a result of fast
temperature change. Microstructure is strongly affected
by the rate of cooling.
Below we will consider the effect of time on phase
transformations using iron-carbon alloy as an example.

18. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 18
Let us consider eutectoid reaction as an example
eutectoid reaction:
γ(0.76 wt% C)
↓
α (0.022 wt% C)
+
Fe3C
The S-shaped curves are shifted to longer times at higher T
showing that the transformation is dominated by nucleation
(nucleation rate increases with supercooling) and not by
diffusion (which occurs faster at higher T).

19. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 19
Isothermal Transformation (or TTT) Diagrams
(Temperature, Time, and % Transformation)

20. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 20
TTT Diagrams
The thickness of the ferrite and cementite layers in pearlite
is ~ 8:1. The absolute layer thickness depends on the
temperature of the transformation. The higher the
temperature, the thicker the layers.
Fine pearlite
Austenite → pearlite
transformation
α ferrite Coarse pearlite
Fe3C
Austenite (stable)
Denotes that a transformation
is occurring
Eutectoid
temperature

21. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 21
TTT Diagrams
The family of S-shaped curves at different T are used to
construct the TTT diagrams.
The TTT diagrams are for the isothermal (constant T)
transformations (material is cooled quickly to a given
temperature before the transformation occurs, and then
keep it at that temperature).
At low temperatures, the transformation occurs sooner
(it is controlled by the rate of nucleation) and grain
growth (that is controlled by diffusion) is reduced.
Slow diffusion at low temperatures leads to fine-grained
microstructure with thin-layered structure of pearlite
(fine pearlite).
At higher temperatures, high diffusion rates allow for
larger grain growth and formation of thick layered
structure of pearlite (coarse pearlite).
At compositions other than eutectoid, a proeutectoid
phase (ferrite or cementite) coexist with pearlite.
Additional curves for proeutectoid transformation must
be included on TTT diagrams.

22. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 22
Formation of Bainite Microstructure (I)
If transformation temperature is low enough (≤540°C)
bainite rather than fine pearlite forms.

23. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 23
Formation of Bainite Microstructure (II)
For T ~ 300-540°C, upper bainite consists of needles of
ferrite separated by long cementite particles
For T ~ 200-300°C, lower bainite consists of thin plates
of ferrite containing very fine rods or blades of cementite
In the bainite region, transformation rate is controlled by
microstructure growth (diffusion) rather than nucleation.
Since diffusion is slow at low temperatures, this phase has
a very fine (microscopic) microstructure.
Pearlite and bainite transformations are competitive;
transformation between pearlite and bainite not possible
without first reheating to form austenite
Upper bainite Lower bainite

24. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 24
Spheroidite
• Annealing of pearlitic or bainitic microstructures at
elevated temperatures just below eutectoid (e.g. 24 h at
700 C) leads to the formation of new microstructure –
spheroidite - spheres of cementite in a ferrite matrix.
• Composition or relative amounts of ferrite and cementite
are not changing in this transformation, only shape of
the cementite inclusions is changing.
• Transformation proceeds by C diffusion – needs high T.
• Driving force for the transformation - reduction in total
ferrite - cementite boundary area

25. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 25
Martensite (I)
• Martensite forms when austenite is rapidly cooled
(quenched) to room T.
• It forms nearly instantaneously when the required low
temperature is reached. The austenite-martensite does
not involve diffusion → no thermal activation is needed,
this is called an athermal transformation.
• Each atom displaces a small (sub-atomic) distance to
transform FCC γ-Fe (austenite) to martensite which has
a Body Centered Tetragonal (BCT) unit cell (like BCC,
but one unit cell axis is longer than the other two).
• Martensite is metastable - can persist indefinitely at
room temperature, but will transform to equilibrium
phases on annealing at an elevated temperature.
• Martensite can coexist with other phases and/or
microstructures in Fe-C system
• Since martensite is metastable non-equilibrium phase, it
does not appear in phase Fe-C phase diagram

26. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 26
The martensitic transformation involves the sudden
reorientation of C and Fe atoms from the FCC solid
solution of γ-Fe (austenite) to a body-centered
tetragonal (BCT) solid solution (martensite).

27. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 27
TTT Diagram including Martensite
Austenite-to-martensite is diffusionless and very fast. The
amount of martensite formed depends on temperature only.
A: Austenite P: Pearlite
B: Bainite M: Martensite

28. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 28
Time-temperature path – microstructure

29. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 29
Mechanical Behavior of Fe-C Alloys (I)
Cementite is harder and more brittle than ferrite -
increasing cementite fraction therefore makes harder, less
ductile material.

30. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 30
Mechanical Behavior of Fe-C Alloys (II)
The strength and hardness of the different microstructures
is inversely related to the size of the microstructures (fine
structures have more phase boundaries inhibiting
dislocation motion).
Mechanical properties of bainite, pearlite, spheroidite
Considering microstructure we can predict that
Spheroidite is the softest
Fine pearlite is harder and stronger than coarse pearlite
Bainite is harder and stronger than pearlite
Mechanical properties of martensite
Of the various microstructures in steel alloys
Martensite is the hardest, strongest and the most brittle
The strength of martensite is not related to microstructure.
Rather, it is related to the interstitial C atoms hindering
dislocation motion (solid solution hardening, Chapter 7)
and to the small number of slip systems.

31. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 31
Mechanical Behavior of Fe-C Alloys (III)

32. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 32
Tempered Martensite (I)
Martensite is so brittle that it needs to be modified for
practical applications. This is done by heating it to
250-650 oC for some time (tempering) which produces
tempered martensite, an extremely fine-grained and
well dispersed cementite grains in a ferrite matrix.
Tempered martensite is less hard/strong as
compared to regular martensite but has enhanced
ductility (ferrite phase is ductile).
Mechanical properties depend upon cementite
particle size: fewer, larger particles means less
boundary area and softer, more ductile material -
eventual limit is spheroidite.
Particle size increases with higher tempering
temperature and/or longer time (more C diffusion)
- therefore softer, more ductile material.

33. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 33
Tempered Martensite (II)
Electron micrograph of tempered martensite
Higher temperature &
time: spheroidite (soft)

34. MSE 300 Materials Laboratory Procedures
University of Tennessee, Dept. of Materials Science and Engineering 34
Summary of austenite transformations
Solid lines are diffusional transformations, dashed is
diffusionless martensitic transformation
Pearlite (α + Fe3C) +
a proeutectoid phase
Bainite
(α + Fe3C)
Slow
cooling
Moderate
cooling
Rapid
quench
Reheat
Tempered martensite
(α + Fe3C)
Austenite
Martensite
(BCT phase)